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Jones AK Lamle SE Pershad HR Vincent KA Albracht SP Armstrong FA 《Journal of the American Chemical Society》2003,125(28):8505-8514
The cycling between active and inactive states of the catalytic center of [NiFe]-hydrogenase from Allochromatium vinosum has been investigated by dynamic electrochemical techniques. Adsorbed on a rotating disk pyrolytic graphite "edge" electrode, the enzyme is highly electroactive: this allows precise manipulations of the complex redox chemistry and facilitates quantitative measurements of the interconversions between active catalytic states and the inactive oxidized form Ni(r) (also called Ni-B or "ready") as functions of pH, H(2) partial pressure, temperature, and electrode potential. Cyclic voltammograms for catalytic H(2) oxidation (current is directly related to turnover rate) are highly asymmetric (except at pH > 8 and high temperature) due to inactivation being much slower than activation. Controlled potential-step experiments show that the rate of oxidative inactivation increases at high pH but is independent of potential, whereas the rate of reductive activation increases as the potential becomes more negative. Indeed, at 45 degrees C, activation takes just a few seconds at -288 mV. The cyclic asymmetry arises because interconversion is a two-stage reaction, as expected if the reduced inactive Ni(r)-S state is an intermediate. The rate of inactivation depends on a chemical process (rearrangement and uptake of a ligand) that is independent of potential, but sensitive to pH, while activation is driven by an electron-transfer process, Ni(III) to Ni(II), that responds directly to the driving force. The potentials at which fast activation occurs under different conditions have been analyzed to yield the potential-pH dependence and the corresponding entropies and enthalpies. The reduced (active) enzyme shows a pK of 7.6; thus, when a one-electron process is assumed, reductive activation at pH < 7 involves a net uptake of one proton (or release of one hydroxide), whereas, at pH > 8, there is no net exchange of protons with solvent. Activation is favored by a large positive entropy, consistent with the release of a ligand and/or relaxation of the structure around the active site. 相似文献
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Self-injection length in La0.7Ca0.3MnO3-YBa2Cu3O7-δ ferromagnet-superconductor multilayer thin films
We have carried out extensive studies on the self-injection problem in barrierless heterojunctions between La0.7Ca0.3MnO3 (LCMO) and YBa2Cu3O7-δ (YBCO) thin films. The heterojunctions were formed in situ by sequentially growing LCMO and YBCO films on 〈100〉 LaAlO3 (LAO) substrate using a pulsed laser deposition (PLD) system. YBCO micro-bridges with 64 μm width were patterned both on
the LAO (control) and LCMO side of the substrate. Critical current, I
c, was measured at 77 K on both the control side as well as the LCMO side for different YBCO film thickness. It was observed
that while the control side showed a J
c of ∼ 2 × 106 A/cm2, the LCMO side showed about half the value for the same thickness (1800 ?). The difference in J
c indicates that a certain thickness of YBCO has become ‘effectively’ normal due to self-injection. From the measurement of
J
c at two different thicknesses (1800 ? and 1500 ?) of YBCO films both on the LAO as well as the LCMO side, the value of self-injection
length (at 77 K) was estimated to be ∼ 900 ?. To the authors’ best knowledge, this is the first time that self-injection length
has been quantified. A control experiment carried out with LaNiO3 deposited by PLD on YBCO did not show any evidence of self-injection. 相似文献
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Study of magnetoresistance and conductance of bicrystal grain boundary in La0.67Ba0.33MnO3 thin film
La0.67Ba0.33MnO3 (LBMO) thin film is deposited on a 36.7°C SrTiO3 bicrystal substrate using laser ablation technique. A microbridge is created across bicrystal grain boundary and its characteristics
are compared with a microbridge on the LBMO film having no grain boundary. Presence of grain boundary exhibits substantial
magnetoresistance ratio (MRR) in the low field and low temperature region. Bicrystal grain boundary contribution in MRR disappears
at temperature T>175 K. At low temperature, I-V characteristic of the microbridge across bicrystal grain boundary is nonlinear. Analysis of temperature dependence of dynamic
conductance-voltage characteristics of the bicrystal grain boundary indicates that at low temperatures (T<175 K) carrier transport across the grain boundary in LBMO film is dominated by inelastic tunneling via pairs of manganese
atoms and tunneling through disordered oxides. At higher temperatures (T>175 K), magnetic scattering process is dominating. Decrease of bicrystal grain boundary contribution in magnetoresistance
with the increase in temperature is due to enhanced spin-flip scattering process. 相似文献
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Molar extinction coefficients of some carbohydrates viz. l-arabinose (C5H10O5), d-glucose (C6H12O6), d-mannose (C6H12O6), d-galactose (C6H12O6), d(-) fructose (C6H12O6) and maltose (C12H24O12) in aqueous solutions have been determined at 81, 356, 511, 662, 1173 and 1332 keV by gamma ray transmission method in a
narrow beam good geometry set-up. These coefficients have been found to depend upon the photon energy following a 4-parameter
polynomial. These extinction coefficients for different sugars having the same molecular formula have same values varying
within experimental uncertainty. Within concentration ranges studied, Beer-Lambert law is obeyed very well. 相似文献
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Hoeben FJ Heller I Albracht SP Dekker C Lemay SG Heering HA 《Langmuir : the ACS journal of surfaces and colloids》2008,24(11):5925-5931
We report on the use of polymyxin (PM), a cyclic cationic lipodecapeptide, as an electrode modifier for studying protein film voltammetry (PFV) on Au and single-walled carbon nanotube (SWNT) electrodes. Pretreating the electrodes with PM allows for the subsequent immobilization of an active submonolayer of [NiFe]-hydrogenase from Allochromatium vinosum ( Av H2ase). Probed by cyclic voltammetry (CV), the adsorbed enzyme exhibits characteristic electrocatalytic behavior that is stable for several hours under continuous potential cycling. An unexpected feature of the immobilization procedure is that the presence of chloride ions is a prerequisite for obtaining electrocatalytic activity. Atomic force microscopy (AFM) relates the observed catalytic activity to enzymatic adsorption at the PM/Au(111) surface, and a combination of concentration-dependent CV and AFM is used to investigate the interaction between the enzyme and the PM layer. 相似文献
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光合细菌Chromatium vinosum可溶性氢酶的EPR研究 总被引:1,自引:0,他引:1
光合细菌 Chromatium vinosum可溶性氢酶经 5次柱层析 ( DE-2 3,TSK-DEAE( ) ,Ultragel Ac A-4 4 ,TSK-DEAE( ) ,Superdex TM75 )分离后被纯化 365倍 ,得率为 32 % ,其催化放氢的活性为 8.4μmol H2 /( min· mg prot) .氧化态可溶性氢酶在 4 5 K下 ,产生了 Ni( )的典型 EPR信号 ( gx,y,z=2 .37,2 .1 6,2 .0 1 6和 gx,y,z=2 .30 ,2 .2 3,2 .0 1 6) ;在 1 0 K下 ,没有出现膜结合态氢酶中存在的 [3Fe-4 S]簇特征 EPR信号 .可溶性氢酶被 H2 还原后 ,Ni( )的特征 EPR信号消失 ,同时出现一个 [4 Fe-4 S]簇的特征 EPR信号 ( gx,y,z=1 .88,1 .90 ,2 .0 4 5 ) .研究结果表明 ,C.vinosum可溶性氢酶在结构和功能上不同于膜结合态氢酶 ,是一种新的催化放氢的 Ni Fe-氢酶 相似文献
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de Alwis SP 《Physical review D: Particles and fields》1992,46(12):5429-5438
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